Introduction: Paraneoplastic syndromes (PNS) may represent the main clinical problem in cancer patients; however, the knowledge of their clinical aspect remains quite poor among urologists. Objective: To provide urologists with an overview on main clinical aspects of PNS that have been reported to be associated to urological cancers. Methods: Literature search of peer-reviewed papers published by July 2008. Results: All genitourinary tumors can cause a PNS, and renal cell carcinoma is the most frequent urological malignancy involved. Prostate cancer is the second urological tumor associated with PNS which, conversely, are uncommon in bladder cancer and rare in testicular cancer. Tumor neuroendocrine differentiation is involved in most endocrine PNS. Neurologic PNS are very uncommon but may dominate the clinical picture and need a high suspicion index to be recognized. Important advances have been made on radionuclide scan methods in order to detect the primary tumor. The most effective treatment strategy is always represented by the radical therapy of the underlying cancer, but specific therapeutic options are sometimes available. Conclusions: Endocrine PNS are frequently associated with urological cancers, especially renal and prostate carcinoma. PNS have been rarely reported in association with cancers of bladder, urethra and testicle.
The increasing global energy demand has stimulated great recent efforts in investigating new solutions for artificial photosynthesis, a potential source of clean and renewable solar fuel. In particular, according to the generally accepted modular approach aimed at optimising separately the different compartments of the entire process, many studies have focused on the development of catalytic systems for water oxidation to oxygen. While in recent years there have been many reports on new catalytic systems, the mechanism and the active intermediates operating the catalysis have been less investigated. Well-defined, molecular catalysts, constituted by transition metals stabilised by a suitable ligand pool, could help in solving this aspect. However, in some cases molecular species have been shown to evolve to active metal oxides that constitute the other side of this catalysis dichotomy. In this paper, we address the evolution of tetracobalt(III) cubanes, stabilised by a pyridine/acetate ligand pool, to active species that perform water oxidation to oxygen. Primary evolution of the cubane in aqueous solution is likely initiated by removal of an acetate bridge, opening the coordination sphere of the cobalt centres. This cobalt derivative, where the pristine ligands still impact on the reactivity, shows enhanced electron transfer rates to Ru(bpy)3(3+) (hole scavenging) within a photocatalytic cycle with Ru(bpy)3(2+) as the photosensitiser and S2O8(2-) as the electron sink. A more accentuated evolution occurs under continuous irradiation, where Electron Paramagnetic Resonance (EPR) spectroscopy reveals the formation of Co(ii) intermediates, likely contributing to the catalytic process that evolves oxygen. All together, these results confirm the relevant effect of molecular species, in particular in fostering the rate of the electron transfer processes involved in light activated cycles, pivotal in the design of a photoactive device.
Intravesical instillation of ONCOFID-P-B for carcinoma in situ refractory to bacillus Calmette-Guérin showed minimal toxicity and no systemic absorption in the first human intravesical clinical trial to our knowledge. Finally, satisfactory response rates were observed.
Light-driven water oxidation is achieved with the Ru(bpy) 3 2+ /S 2 O 8 2− cycle employing the highly active Ir-blue water oxidation catalyst, namely, an Ir IV,IV 2 (pyalc) 2 μ-oxo-dimer [pyalc = 2-(2′-pyridyl)-2-propanoate]. Ir-blue is readily formed by stepwise oxidation of the monomeric Ir(III) precursor 1 by the photogenerated Ru(bpy) 3 3+ , with a quantum yield ϕ of up to 0.10. Transient absorption spectroscopy and kinetic evidence point to a stepwise mechanism, where the primary event occurs via a fast photoinduced electron transfer from 1 to Ru(bpy) 3 3+ , leading to the Ir(IV) monomer I 1 (k 1 ∼ 10 8 M −1 s −1 ). The competent Ir-blue catalyst is then obtained from I 1 upon photooxidative loss of the Cp* ligand and dimerization. The Ir-blue catalyst is active in the Ru(bpy) 3 2+ /S 2 O 8 2− light-driven water oxidation cycle, where it undergoes two fast photoinduced electron transfers to Ru(bpy) 3 3+ [with k Ir-blue = (3.00 ± 0.02) × 10 8 M −1 s −1 for the primary event, outperforming iridium oxide nanoparticles by ca. 2 orders of magnitude], leading to a Ir V,V 2 steady-state intermediate involved in O−O bond formation. The quantum yield for oxygen evolution depends on the photon flux, showing a saturation regime and reaching an impressive value of ϕ(O 2 ) = 0.32 ± 0.01 (corresponding to a quantum efficiency of 64 ± 2%) at low irradiation intensity. This result highlights the key requirement of orchestrating the rate of the photochemical events with dark catalytic turnover.
Intravesical Bacillus Calmette-Guérin (BCG) is the gold standard treatment for intermediate and high-risk non-muscle-invasive bladder cancer. BCG therapy is the most successful example of immunotherapy in cancer. Unfortunately, the treatment-related side effects are still relevant. Furthermore, non-responder patients are candidate to radical cystectomy in the absence of valuable alternative options. These aspects have prompted the search for newer biological response modifiers (BRM) with a better benefit/side effects ratio. The toll-like receptor (TLR) 2 ligand, Helicobacter pylori protein HP-NAP, has been shown to deserve a potential role as BRM. HP-NAP is capable of driving the differentiation of T helper (Th) 1 cells, both in vitro and in vivo, because of its ability to create an IL-12-enriched milieu. Herein, we report that local administration of HP-NAP decreases tumour growth by triggering tumour necrosis in a mouse model of bladder cancer implant. The effect is accompanied by a significant accumulation of both CD4+ and CD8+ IFN-γ-secreting cells, within tumour and regional lymph nodes. Noteworthy, HP-NAP-treated tumours show also a reduced vascularization due to the anti-angiogenic activity of IFN-γ induced by HP-NAP. Our findings strongly indicate that HP-NAP might become a novel therapeutic "bullet" for the cure of bladder tumours.
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